Herbicidal benzyl alcohols

ABSTRACT

Ethyl triisopropyl benzyl alcohols 2,4,6- and 2,4,5-) and mixtures thereof are disclosed which may be applied to the soil to preclude the establishment of weeds in the soil. These compounds are particularly effective in preventing the establishment of crabgrass.

United States Patent 191 Lavanish HERBICIDAL BENZYL ALCOHOLS [75] Inventor: Jerome M. Lavanish, Akron, Ohio [73] Assignee: PPG Industries, lnc., Pittsburgh, Pa. 221 Filed: July 25, 1973 [21] App]. No: 382,630

Related U.S. Application Data [63] Continuation-impart of Ser, No. 264,683, June 20,

1972, abandoned.

OTHER PUBLICATIONS Fuson et al., J. Am. Chem. Soc, Vol. 64, pp 30-33 51 Oct. 7, 1975 Nightingale et all Chem. Absti" Vol 44, 3462f (I950).

Beets "Chem. Abstract," Vol. 45 9502b (1951).

Bansol et al. Chem. Abstract, Vol. 65, [837d (1966) Primary ExaminerDonald G Daus Assistant E.raminer-D. B. Springer Attorney. Agent, or FirmR0bert J Grassi; Mark Levin [57] ABSTRACT Ethyl triisopropyl benzyl alcohols 2,4.6- and 2 4,5-) and mixtures thereof are disclosed which may be applied to the soil to preclude the establishment of weeds in the soil. These compounds are particularly effective in preventing the establishment of crabgrass 3 Claims N0 Drawings HERBICIDAL BENZYL ALCOHOLS CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of my copending application Ser. No. 264,683, filed June 20, 1972. This application which is assigned to PPO IN- DUSTRIES, INC. is related to PPG INDUSTRIES, INC. allowed co-pending application Use of Herbicidal Benzyl Alcohols, Ser. No. 382,623 filed even date herewith which describes methods of using herbicidal benzyl alcohols for control of weeds particularly crabgrass, and to PPG INDUSTRIES, INC. allowed copending application entitled, Herbicidal Chlorinated Benzyl Alcohols, Ser. No. 264,684, filed June 20, 1972 which describes l-chloromethyl 2',4',6 triisopropylbenzyl alcohol, and the use of herbicidal chlorinated benzyl alcohols for control of weeds.

In accordance with this invention there are provided particular benzyl alcohols which are effective in controlling weeds. One or more benzyl alcohols may be applied to the soil in an amount effective to preclude the establishment of weeds in the soil. Benzyl alcohols here contemplated include those represented by the formula:

C H HOH The above compounds are especially effective against annual grasses, particularly small-seeded annual grasses, such as crabgrass (Digitaria sanguinalis). Consequently, crabgrass or other annual grasses may be controlled by applying to the soil an amount of one or more of the benzyl alcohols effective to preclude the establishment of crabgrass or other annual grasses in the soil.

Compounds which exemplify the benzyl alcohols of the present invention are:

l-ethyl-2 ',4,5 -triisopropylbenzyl alcohol and,

l-ethyl-2,4',6'-triisopropylbenzyl alcohol.

Mixtures of these compounds may be used.

These benzyl alcohols may be prepared by the reduction of the appropriate alkyl aryl ketones. One particularly useful reducing agent for this purpose is lithium aluminum hydride. The reaction may conveniently be conducted in a solvent.

Many of the alkyl aryl ketones used to prepare the benzyl alcohols are known to the art. In those instances where the compounds having the desired substitutions are not available, they may be prepared by any of the methods well known in chemistry. One of these is the reaction, in the presence of aluminum chloride, of a substituted benzene with an acyl chloride.

The benzyl alcohols may be prepared by the reaction of the appropriate aryl Grignard reagent with the appropriate aldehyde. For example, l-ethyl-2',4',6'- triisopropylbenzyl alcohol may be prepared by reacting 2,4,6-triisopropylphenyl magnesium bromide with propionaldehyde in the presence of a diethyl ether solvent. Illustrative preparations of the benzyl alcohols are shown in Examples I IV:

EXAMPLE I 2' ,4 ,6 -Triisopropylpropiophenone A 3000-milliliter, three-necked flask was fitted with a mechanical stirrer, addition funnel, and reflux condenser with drying tube. The flask was cooled in an ice bath and charged with I333 grams l .00 mole) of aluminum chloride in 500 milliliters of carbon tetrachloride. Then 102 grams (l.l0 mole) of propionyl chloride in 500 milliliters of carbon tetrachloride was added. The addition funnel was charged with 204 grams (1.00 mole) of l,3,5-triisopropylbenzene in 300 milliliters of carbon tetrachloride. The funnel solution was added dropwise over 260 minutes at the ice bath temperature while vigorous stirring was maintained. The yellow-green slurry was stirred for an additional I20 minutes and then poured into 600 grams of icev After the ice melted the layers were separated and the organic phase was washed with 1000 milliliters of water and then with 500 milliliters of five percent sodium bicarbonate solution and then dried over anhydrous magnesium sulfate. Removal of the solvent in a rotary film evaporator gave 244.3 grams of crude 2',4, 6'-triisopropylpropiophenone as moist pale yellow crystals. This was used without further purification. The product may be depicted as having the structural formula:

l-Ethyl-2',4',6'-triisopropylbenzyl Alcohol A 3000-milliliter flask was outfitted as previously described. The flask was charged with l9.0 grams (0.50 mole) of lithium aluminum hydride in 1000 milliliters of dry ether. The addition funnel was charged with the 244.3 grams (0.938 mole) of the previously prepared triisopropylpropiophenone in 400 milliliters of dry ether. The addition was made dropwise at room temperature over 350 minutes. Stirring was continued overnight, after which the reaction mixture was heated to reflux for l 10 minutes. After cooling there was then added dropwise l9 milliliters of water, 19 milliliters of 15% sodium hydroxide solution, and then 57 milliliters of water. Celite diatomaceous earth was then added to aid in filtering and this slurry was then suction filtered through a bed of magnesium sulfate. The filter cake was washed with two milliliter portions of ether and solvent was removed from the combined filtrate in a rotary film evaporator to give 237.4 grams of crude l-ethyl-2,4,6-triisopropylbenzyl alcohol. The crystals were dissolved in 400 milliliters of hot hexane and then placed in a freezer to facilitate crystallization. The crystals were suction filtered and dried at 50C. and 40 millimeters Hg. They weighed 202.4 grams and had a melting point range of 98C. l02.5C. The product may be depicted as having the structural formula:

( HzIlQ C A 3000-milliliter, four-necked flask was equipped with a mechanical stirrer, addition funnel, stopper, and reflux condenser with drying tube. The flask was charged with 147 grams 1 mole) of aluminum chloride and 500 milliliters of carbon tetrachloride and cooled in an ice bath. Then 102 grams (1.10 mole) of propionyl chloride in 500 milliliters of Carbon tetrachloride were added. The addition funnel was charged with 204 grams 1.00 mole) of 1.3,5-triisopropylbenzene which was added with stirring over a period of about 2 hours. The mixture was stirred at ice bath temperature for 3 hours and then poured over 1000 grams of crushed ice. The flask was rinsed with 50 milliliters of carbon tetrachloride and 50 milliliters of water which were added to the ice slurry. After the ice had melted the two liquid phases were separated and the organic layer was washed with 1000 milliliters of water and 500 milliliters of 5% sodium bicarbonate solution. After drying over magnesium sulfate. the organic phase was filtered. Solvent was removed from the filtrate in a rotary film evaporator at 50C. and 20 millimeters Hg to give 255.6 grams of pale yellow crystals having a melting point range of 815C. 84C. which were used without further purification. Repetition of the above procedure two more times yielded 257.3 grams of crystals having a melting point range of 82C. 84C. and 256.7 grams of crystals having a melting point range of 83C. 84C.

l-Ethy1 2',4',o'-triisopropylbenzyl Alcohol A 3000-mi1lilitcr. three-necked flask was fitted with a mechanical stirrer. addition funnel, and reflux condenser with drying tube. The flask was charged with 9.5 grams (0.25 mole) of lithium aluminum hydride in 1000 milliliters of anhydrous ether. The addition funnel was charged with 1302 grams (0.500 mole) of triisopropylpropiophenone in 300 milliliters of dry ether which was added with stirring over a period of about 2 hours. The slurry was then heated to reflux for about 2 hours. After cooling. 9.5 milliliters of water, 9.5 milliliters of sodium hydroxide solution. and 28.5 milli liters of water were added dropwise. The slurry was then suction filtered through a bed of magnesium sulfate. Solvent was removed from the filtrate in a rotary film evaporator at about 50C. and millimeters Hg to give 128.2 grams of white powder. The above procedure was repeated five more times to give the following weights of product: 126.5 grams. 127.2 grams, 127.5 grams, 1252 grams. and 1272 grams. respectively.

EXAMPLE lll l-Ethyl-2,4',6'-triisopropylbenzyl Alcohol A 500-milliliter. three-necked flask was equipped with a mechanical stirrer and a continuous extractor with a reflux condenser equipped with drying tube. The flask was charged with 65.5 grams (0.25 mole) of 2,4- ',6'-triisopropylpropiophenone in 250 milliliters of dry ether. The extractor was charged with 2.9 grams oflithium aluminum hydride. The contents of the flask were refluxed with stirring over a period of about 9 hours. The extractor was then charged with an additional 2.9 grams of lithium aluminum hydride. The contents of the flask were refluxed with stirring over a period of about 12 hours. The extractor was replaced with a reflux condenser and an addition funnel was affixed to the flask. After cooling by the successive addition of 6 milliliters of water, 6 milliliters of 15% sodium hydroxide. and 18 milliliters of water, the resulting slurry was then suction filtered through a bed of magnesium sulfate. The solvent was removed from the filtrate on a rotary film evaporator to give 57.9 grams of white solid. Recrystallization from normal hexane gave 47.4 grams of crystals having a melting point range of 99C. 102C. The product may be depicted as having the structural formula:

IHECHH H oH :ll2 CH[CH3)2 l nh EXAMPLE 1V 2,4',5 '-Triisopropylpropiophenone and 2,4' ,6 '-Triisopropylpropiophenone A l000-milliliter, three-necked flask was equipped with a mechanical stirrer, addition funnel, and reflux condenser with drying tube. The flask was immersed in an ice bath and charged with 28.0 grams (0.21 mole) of aluminum chloride and 1000 milliliters of carbon tetrachloride. Propionyl chloride in the amount of 20.4 grams (0.22 mole) in milliliters of carbon tetrachloride was then added to the flask. The addition funnel was charged with 49.3 grams (0.20 mole) of 1.2,4,S-tetraisopropylbenzene and milliliters of carbon tetrachloride which were added with stirring over a period of about 100 minutes. The resulting brick-red slurry was stirred at ice bath temperatures for 2 hours and then poured over 500 grams of crushed ice. After the ice had melted. the layers were separated. The organic phase was washed with 200 milliliters of water and 200 milliliters of 5% sodium bicarbonate solution and then dried over magnesium sulfate. Removal of the solvent in a rotary film evaporator gave 50.8 grams of viscous yellow oil which partially crystallized on standing. Two recrystallizations from cold normal hexane gave 22.9 grams of white crystals having a melting point range of 47C. 62C. Vapor phase chromatographic analysis (5 feet by A inch SE 30 column with 20% by weight loading, 210C, 60 milliliters of helium per minute) showed two components. The first, 2',4',6"triisopropylpropiophenone, had a retention time of 4.8 minutes relative to the air peak and the second component, 2',4,5'-triisopropylpropiophenone,

had a retention time of 6.1 minutes relative to the air peak. The peak area ratio of the first component to the second component was about 112.5. Several hundred milligrams of each of the above components were collected by preparative vapor phase chromatography using an 8 feet by /5 in Carbowax M. column at 220C. The 2' ,4,6'-triisopropylpropiophenone sample had a melting point range of 58C. 81C. and the 2',4,5'-triisopropylpropiophenone sample had a melt ing point range of 5lC. 69C. The 2',4',6'-triisopropylpropiophenone may be depicted as having the structure:

cum-1,,

(C sh CH(CHHJ2 The 2',4',5-triisopropylpropiophenone may be depicted as having the structure:

l-Ethyl-2',4',5 -triisopropylbenzyl Alcohol A SO-milliliter, three-necked flask was equipped with a mechanical stirrer, addition funnel, and reflux condenser with drying tube. The flask was charged with 0.07l grams (0.0019 mole) of lithium aluminum hydride in 8 milliliters of dry ether. The addition funnel was charged with 0.76 grams of 2',4','5'-triisopropylpropiophenone in 8 milliliters of dry ether. This was added dropwise over a period of about 5 minutes. The slurry was then stirred at room temperature for minutes and then heated to reflux for ISO minutes. After cooling, there were added sequentially with stirring 7() .l of water, 70pl of 1571 sodium hydroxide solution, and 210a] of water. Celite diatomaceous earth filter aid was then added, and the reaction mixture was suction filtered through a bed of magnesium sulfate. Removal of solvent in a rotary film evaporator gave 0.56 gram of waxy white solid having a melting point range of 66C. 75C. The product may be depicted as having the structural formula:

H OH

One or more of the above benzyl alcohols may be applied to the soil in an amount effective to preclude the establishment of weeds, particularly annual grasses such as crabgrass, in the soil. The establishment precluded is with respect to mature weeds or weeds sufficiently advanced in growth to significantly interfere with the growth of desirable plants; mere germination of weed seeds to produce tender seedlings which are susceptible to attack by the benzyl alcohols is not establishment" as used herein.

The amount of the benzyl alcohol applied to the soil may vary widely. The amount applied usually is in the range of from 0.1 to 100 pounds per acre. Usually the amount is in the range of from 0.] to 50 pounds per acre or even in the range of from 0.5 to 20 pounds per acre. Application in the range of from 0.5 to [0 pounds per acre is preferred. While these ranges are generally applicable, it is recognized that both optimum and useful amounts will vary depending upon the crop plant involved, if any, the weeds encountered, the particular compound used, the soil condition, cultivation practices, and the effect desired. The Examples give an even better indication of the amounts of the benzyl alcohols which may advantageously be used when dealing with certain weeds. The above-mentioned benzyl alcohols may be formulated in many ways. Convenient formulations include granular formulations, wettable powders, solutions, and emulsions. These formulations may be prepared in accordance with the general techniques well known to the art. These formulations may be applied directly to the soil or they may be diluted before application.

Generally speaking, formulations contain from about 0.1 to I00 percent by weight of the benzyl alcohol. Often formulations contain from about 1 to about 50 percent by weight of the benzyl alcohol. Of course, the precise amount will depend upon such factors as the type of formulation employed, the type of application, and the mode of application.

Suitable wettable powders typically contain from about 1 to about 100 percent by weight of the benzyl alcohol. Ordinarily wettable powders contain from 10 to percent by weight of the benzyl alcohol. The benzyl alcohol may be admixed with an inert powder such as silica, chalk, talc, limestone, or clay. Any convenient amount of diluent may be used, from about 15 to about percent being typical. Small amounts of dispersing and/or wetting agents are usually included in the formulations. These usually range from 0.l to l5 percent by weight of the formulation. Ordinarily amounts ranging from 1 to 12 percent are used. The wettable powder is typically dispersed in water for application.

Solutions of the benzyl alcohol or alcohols may be prepared. Ordinarily concentrated solutions are prepared which, when diluted with water for application, form emulsions. Solvents suitable for use are numerous and include many well known for their solvency powers. Examples include the xylenes, toluene, methyl alcohol, ethyl alcohol, isopropyl alcohol, the butyl alcohols, water, gasoline, kerosene, diethyl ether, methyl ethyl ether, ethylene glycol, propylene glycol, n-amyl acetate, allyl alcohol, Cello-Solve, methyl acetate, ethyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, benzene, methyl naphthalene, ethyl naphthalene, and edible oils such as corn oil, olive oil, cod liver oil, cottonseed oil, safflower oil, soybean oil, and peanut oil.

The formulations of the present invention frequently include small amounts of various surfactants such as wetting agents, emulsifiers, and dispersants. Anionic surfactants are used for wettable powders. Emulsifiable concentrates generally contain blends of ionic and anionic surfactants. Many surfactants are available as commercial products. Well known dispersing agents which are useful in wettable powders include the lignin surfactants (ligno sulfonates) such as those described in US. Pat. No. 2,491,832, and the alkaryl sulfonates. The ligno sulfonates of most interest are the metallic, notably the sodium and calcium, sulfonate salts. Molecular weights of these materials normally range from about 1,000 to about 20,000. Another useful class of surfactants comprises the formaldehyde-naphthalene sulfonate condensates typified by those disclosed in US. Pat. No. 2,516,095. Other useful dispersing agents are found among the alkali metal derivatives of unsaturated and aromatic hydrocarbons, the alkali metal alcoholates of long chain alcohols, and the anhydrous alkali metal soaps of higher fatty acids. Particularly suitable wetting agents for wettable powders are the taurates typified by sodium N-methyl-N-oleoyl taurate. Sodium alkyl naphthalene sulfonates and the oleic acid ester of sodium isothionate are also especially useful. The condensation products of alkylene oxides with phenols and organic acids, the polyalkylene derivatives of sorbitan esters, complex ether alcohols, and mahogany soaps are examples of useful ionic surfactants. Other surface-active agents of the same or similar physical properties are known to the art and can be employed in the formulations of this invention.

It is often desirable to include in a formulation which is to be mixed with water a small amount e.g., about l/l to about 1 percent by weight of a suitable antifoaming agent. Useful anti-foaming agents include the ditertiary acetylenic glycols, such as those marketed under the tradename SURFYNOU by Air Reduction Chemical and Carbide Company, 150 E. 42nd Street, New York, NY. 100l7. Other compounds known to the art to function as anti-foaming agents may be employed if desired. Such compounds include 2-octonol, sulfonated oils, and silicones. Useful silicones are those of low molecular weight, i.e., the silicone fluids or oils. Typical of these are the methyl and ethyl substituted siloxanes such as the dimethyl siloxanes.

Many of the solvents, solvent systems, and wetting agents are discussed in US. Pat. Nos. 2,695,225 and 3,330,642 and Canadian Patent 851,658.

The amount of the benzyl alcohol in liquid formulations, including both single-phase solutions and emulsions, is subject to wide variation. The liquid may contain the benzyl alcohol in very dilute concentrations although it is ordinarily not so dilute that excessive amounts of solvent must be applied in order to achieve application of a useful amount of the benzyl alcohol. The lowest practical concentration for most purposes is the concentration at which the formulation is applied to the soil. The upper limit of concentration is the solubility limit of the benzyl alcohol in the solvent or solvent system used. This will, of course, depend upon the identity of the benzyl alcohol, the identity of the solvent system, and the highest temperature for which precipitation of solids is acceptable. It is ordinarily desirable to from a concentrated liquid formulation, usually an emulsifiable concentrate or concentrated emulsion, of the benzyl alcohol which will not show precipitation above about 20F. and, more preferably, above about 10F. A broad range of concentration for the benzyl alcohol in a liquid formulation is from 0.05 percent to 90 percent by weight. Liquid concentrates generally contain from about 10 percent to about percent by weight of the benzyl alcohol. From about 35 percent to about 55 percent is preferred. Liquid formulations generally contain from about 0.05 percent to about 70 percent of the benzyl alcohol at the time of application. Typically, the range is from 0.1 to 10. From about 0.5 percent to 5 percent is preferred.

Granular formulations may be prepared by spraying the molten benzyl alcohol directly onto an inert carrier. In another method, a liquid formulation, either a solution or an emulsion, may be applied to the inert carrier particles. Many types of inert carrier particles are suitable for use in the instant invention. Among these are montmorillonite, bentonite, vermiculite, corn cobs, and sawdust. The benzyl alcohol ordinarily constitutes from about 0.5 to about 50 percent by weight of these granular products. Typically, the benzyl alcohol content ranges from about 1 to about 35 percent by weight. From about 10 to about 30 percent is preferred.

In the following examples, test plants are abbreviated according to the following key:

C ro SU BT CORN OATS CLVR SOYB COTN WH'T PNUT RICE KYBG ALFA FLAX Weeds YNSG WOAT J MWD VTLF JNGS PlGW MSTD Sugar Beet (Bela vulgaris, L.) Corn (Zeu muyx, L.)

Oats (Arena saliva, L.)

Red Clover (Trlfolium prawns", L.) Soybean (Glycine max [L.| Merr.) Cotton (Gm-.rypium hirxumm, L.) Wheat ('I'riricunl uesrirum, 1..) Peanut (Amt/us hypogaeu. L.)

Rice (Oryzu sum-u, L.)

Kentucky Bluegrass (P01! prurensis, L.) Alfalfa (Mei/Inigo .vulim, L.)

Flax (Linum ulsl'mrissimunl, L.)

Yellow Nutsedge (Cyperus escu/eumx, L.)

Wild Oats (Arena fama, L.)

Jimsonwced (Datum slranwnium, L.)

Velvetleaf (Ahurilon llieophrasri, Medic.)

Johnsongrass (Sorghum hulepem v, Pers.)

Pigwecd (Amuramhus relroflexus, L.)

Mustard (Bmrsicu kaber, L. C. Wheeler, Var.

pinuurifidu, L. C. Wheeler) Yellow Foxtail (Selariu gfum'u [L] Beauv.)

Barnyard grass (Edlinochlau crusgalfi, Beauv.)

Crabgrass (Digilariu sauguinulis IL.) Scop.)

Buckwheat (Pulygmlum com'olvulus, L.)

Morning Glory (Mixture of Ipumoea purpurea, Roth and Iponioeu hederac'eu, Jacq Quackgrass (Agropyrorl repens I L.) Beauv.)

Giant Foxtail (Seraria fuberii, Herrm.)

Cocklebur (Xanrlu'um pumsyfvunicum, Wallr.)

C heatgrass (Bmmus (1110mm, L.)

Green Foxtail (Serariu \iridis IL.) Beauv.)

Purple Nutsedge (Cyperus rorundus, L.)

Fall Panicum (Pum'cum dic/zluromrflorum, Michx.)

Canada Thistle (Cirsium urvense [L.] Scop.)

Lambsquarter (Chelmptxlium album, L.)

Switchgrass (Punicum virgulum, L.)

Annual Ryegrass (Lolium "mini/10mm, Larn.)

YLF X BNGS C 805 BKWT MNGY QKGS GTFX C KBR C'TGS GNFX PNSG FPAN CT HS LMQR SWGS ARYE All plants are grown from seeds unless otherwise indicated:

(R) grown from rhizomes (T) grown from tubers EXAMPLE V Test compound is formulated in a solvent mixture acetone, 8% methanol, and 2% dimethylformamide by volume) to form a solution. Appropriate weed species are seeded in individual disposable, threeinch square containers containing about 2 inches of soil. A small amount of sand, usually V8 to V4 inch in EXAMPLE VI] The procedure of Example V is repeated using I- Table 3 Injury Ratings of Test Plants After Treatment With 1 -Ethyl-2' ,4 ,fi Triisopropylbenzyl Alcohol Holding Period, Days After Application per acre Crops compound applied at lower rates to both crop plants and weed plants. The identities of the test plants, holding periods, rates of application. and results are shown in Table 3.

Test

Plants Rate, pounds SUBT CORN OATS CLVR sova COTN 25 WHT PNUT this procedure, 1, ',6-trimethyl-4'-tbutylben zyl alcohol was evaluated. The identities of the Table l depth, is applied to cover the seeds. The containers are placed on carrying trays and the carrying trays of containers are then placed on a conveyor belt having a linear speed of 1.3 miles per hour. As each tray is moved along on the conveyor it trips 3 mlcroswllch 5 ethyl-2',4,6'-triisopropylbenzyl alcohol as the test which, in turn, activates a solenoid valve and rele' the solution of the test as sprays at the rate of 50 gallons per acre. The test compounds are immediately watered in and the containers then removed to the greenhouse and held for observation. Treatments are observed [0 daily for interim response, final observations being made at the conclusion of the holding period. Any treatments inducing especially significant responses are held beyond the regular holding period until such responses can be confirmed. Each result is reported as an Injury Rating which is represented as follows: 0no visible effect; 1,2, or 3-slight injury, plant usually re covered with little or no reduction in top growth; 4, 5, or 6moderate injury, plants usually recovered but with reduced top growth; 7,8, or 9severe injury, plants usually did not recover; l0complete control.

Using test plants, holding periods, rate of application, and results are shown in Table l.

.l m .m mm n g d n ed w 0600 00 70050600 m O ut m m e m n 0900 0079U0 07 m m M th 0 l (t m 0(2439876w30 e s l A warm T @m I T rm s im 00 0089m090700 S S at TnrSA E il 8 u mm T. v s G Mfl Mfl N n m 4 W I 6 f wrPHsM 002335796030 0 00 00680080 06 0 d m 0 b mww v. I E m ys o b a m a n 4 Him m X mm m T a? 00 0 00880080804 P E m TKM I l M :m w e mfit "Hum D. Ta T m U B a m f a F SS Y 0 5 0488m29 904 M6 0 mm H e m m Y WJHMYBCM mflm r m. T l 2 u .m m 0 m wm m x s RSX e b. amfimm mm wmm w mm s axA wommocmo Fmm mwWT 0 5 0 5 3 3 4 4 fi w fi nmmrm .l 000080285900 m n m m mo m m m m m m W a .1 0 2202080388m00 ..m m wmm w no .mO 000225202820 a d mm c 2 w cow mA mm o e man al ehtl mAu 5524294599000 cv. an. r. e s l .12 r .V flm A ktp Tum r l i. a r r. m mv m V V m 20208 385900 AuemA E i 2 v. w EIWWHWB 000005503922 L m a P pim M mW 2224082588m00 Paw M m ab a m mm MP A x um T m m u X E u c Th O 1 H .m E f m ft 5625285588000 SW 5 T o dp 011" l m m mro 0 Y ewia a P5 X nfl m H mm mwfimmmm wfm r Ywmw MY cBM m6 m i 6 l T 3 r r. m4 m i mm l pr u i .m r 2 0& WWW l .p 6 D. TD Y h Ol T mi mm wmmmm m fk l eCPT TP R YWMWWPMYBCMM COMPARISON TEST B The procedure of Example V is repeated using L2,- 4',6'-tetraisopropylbenzyl alcohol as the test compound. The identities of the test plant, holding periods. rate of application. and results are shown in Table 5.

Table 5 Injury Ratings of Test Plants After Treatment With l 2',4' 6-Tctraisopropylhcnzyl Alcohol at ll) Pounds Per Acre Holding Period,

COMPARISON TEST C The procedure of Example V is repeated using 1- propyl 2',4',6'-triis0propylbenzyl alcohol as the test compound. The identities of the test plants, holding periods. rate of application, and results are shown in Table 6,

Table 6 lnjur Ratings of Test Plants After Treatment With LPropyLZ'.4 fi'-triisopropylhenzyl Alcohol at Ill Pounds Per Acre Holding Period Days After Application I4 23 Test Plants YNSG (T) WOAT JMWD .INGS

PIGW MSTD BNGS (BGS BKWT MNGY COMPARISON TEST D The procedure of Example V is repeated using I- methyl-2',4',6'-triisopropylbenzyl alcohol as the test compound applied at lower rates. The identities of the test plants. holding period. rates of application, and results are shown in Table 7.

Table 7 lnjur Ratings of Test Plants [3 Days After Treatment With l-McthyLZ.4.6'-triisopropylbenzyl Alcohol Table 7-Continued Injury Ratings of Test Plants I3 Days After Treatment With 1-Mcthyl-2.4'.6'-triisopropylbenzyl Alcohol Test Plants Rate. Pounds Per Acre YLFX 7 3 3 BNGS 7 5 2 C865 9 3 1 BKWT (J (J U MNGY O (J O COMPARISON TEST E The procedure of Example V is repeated using 1,2,- 4',6'-tetraisopropylbenzyl alcohol as the test compound applied at lower rates. The identities of the test plants. holding period, rates of application, and results are shown in Table 8.

Table 8 Injury Ratings of Test Plants 13 Days After Treatment With I ,2 .4 6'-Tetraisnpropylbenzyl Alcohol Test Plants Rate. Pounds Per Acre YNSG (T) (I U (l WOAT l) [I ll JMWD U 0 U VTLF U (I U .INGS U 0 PIGW U U U MSTD 4 0 (l YLFX 6 4 l BNGS 3 l CBGS 9 7 2 BKW'T (J O 0 MNGY (I O COMPARISON TEST F The procedure of Example V is repeated using I- propyl-2',4,6'-triisopropylbenzyl alcohol as the test compound applied at lower rates. The identities of the test plants, holding periods, rates of application, and results are shown in Table 9.

Table 9 Injury Ratings of Test Plants After Treatment With l-Propyl-2' 4',6'-triisopropylbenzyl Alcohol Test Plants Holding Period, Days After Application Rate. pounds per acre 5 2 l S 2 l Crops YNSG (T) O O (l U U 0 WOAT U 0 U 0 O .IMWD Z Z O O 0 U VTLF 3 2 l O O O JNGS l 0 O 0 U 0 PIGW 2 2 2 0 0 O MSTD 4 2 0 4 0 O YLFX 9 8 4 9 S 0 BNGS 8 8 0 5 2 0 (B05 9 9 5 9 8 5 BKWT I O O O O O MNGY I O O O 0 0 EXAMPLE VIII The procedure of Example V is repeated using a mixture of l-ethyl-2,4',6'-triisopropylbenzyl alcohol and l-ethyI-2',4',5'-triisopropylbenzyl alcohol in a 3:2 molar ratio as the test composition. The identities of The rates of application and the results are shown in Table l I.

Table l l injury Ratings of Test Plants Two Weeks After Treatment With Various Bcnzyl Alcohols l pound per acre 2 pounds per acre Test Compound SWGS (TGS YLFX WOAT CBGS ARYE SWGS CTGS YLFX WOAT CBGS ARYE Control U (1 0 (J (J (J (J (J 0 (l U Ethyl-2',4,5-triisol 2 2 (J 9 S 8 3 8 4 ll) 6 propylbenzyl Alcohol 2 2 0 9 6 S 4 8 6 It) 4 l-Ethyl-2,4',6'-trii i 2 (1 6 6 I0 5 8 2 9 R isopropylbcnzyl Alcohol 5 I 0 0 9 8 7 9 8 4 It) 7 l-Ethyl-2'.4',6-triiso- 7 i 3 U 9 5 9 7 7 l) H) 9 propylbenzyl Alcohol 7 i Z 2 9 6 HI 7 8 2 HI 9 5 pounds per acre Test Compound Control U t) O 0 (J (J l-Ethyl-Z'.4',S-triisol(] 9 9 8 l0 8 propylbenzyl Alcohol l0 l() 9 7 l0 7 l-EthyI-ZAZN-Iri' 9 8 9 7 ll) l0 isupropylhcnzyl Alcohol It] 9 9 7 l0 l0 l-Ethyl2',-l',6'-triiso H] 7 9 6 l0 l0 propylbenzyl Alcohol l0 8 9 4 l0 10 Table I0 EXAMPLE Xll Test Plants YNSG (T) WOAT .I MWD VTLF J NGS LMQR MSTD YLFX BNGS C BGS BKWT MNGY ccEcccu-Hecx EXAMPLE lX A soil mixture (2 parts sandy loam, l part sand) was placed into pots. Pots were then seeded with switchgrass, cheatgrass, yellow foxtail, wild oats, crabgrass, and annual ryegrass. Immediately after planting, the soil surfaces were sprayed with the test compound 1- ethyl-2',4',6'-triisopropylbenzyl alcohol dissolved in milliliter of a solvent mixture (90% acetone, 8% methanol, and 2% dimethylformamide by volume). The sprayed pots were placed under light banks and rated 2 weeks after application of the test compound. The plant injury ratings were expressed on a scale ranging from 0 (no effect) to 10 (complete kill). All treatments were applied in duplicate. The rates of application and the results are shown in Table l 1.

EXAMPLE X The procedure of Example IX is repeated except that l-ethyl-2',4',5'-triisopropylbenzyl alcohol is used as the test compoundv The rates of application and the results are shown in Table l 1.

EXAMPLE XI The procedure of Example lX is repeated except that l-ethyl-Z',4,6-triisopropylbenzyl alcohol prepared from a different source is used the test compound.

In the late spring, purchased Merion bluegrass (Pm: pratensis, L. var. Merion) sod was laid down to form 10 feet by 3 feet plots. The sod was allowed to become established and l4 days after the sod was laid the plots were seeded with crabgrass (Digimriu sunguinulis [L.] Scop.) The seeds were then raked in the grass and the plots sprayed with solutions of l-ethyl-2',4-6-triiso propylbenzyl alcohol. The sprayer covered a 4-foot wide strip; therefore, the amount of compound sprayed on the plots was calculated based on 40-square-feet plots. Treatments applied to the seeded plots on the day of seeding were:

1. Control not seeded with crabgrass.

2. Control seeded with crabgrass.

3. l-Ethyl-2',4',6-triisopropylbenzyl Alcohol at 5 pounds per acre.

4. l-Ethyl-2',4,6-triisopropylbenzyl Alcohol at pounds per acre.

5. l-Ethyl-2,4,6-triisopropylbenzyl Alcohol at 1 pound per acre.

The plots were examined for emergence of crabgrass 3 weeks after spraying. None of the plots, treated or untreated, contained any crabgrass. The sod was not treated by the sod grower with any crabgrass herbicide and the sown crabgrass was viable; therefore, only the good quality, condition, and density of the sod prevented the growth of crabgrass in the untreated plots.

Fifty-eight days after laying the sod, the sod plots were distressed and severely damaged by using a rotary tiller to decrease turf density. All the previously treated and some untreated plots were then reseeded with crabgrass and two previously untreated plots were treated with solutions of l-ethyl-2',4',6'-triisopropylbenzyl alcohol at 2 pounds per acre and 5 pounds per acre, respectively.

Three weeks after reseeding of the thinned sods the plots were examined for emergence of crabgrass. Observations substantiated the previously suggested reason for the lack of crabgrass in the plots, since after thinning there was a significant number of crabgrass plants in several of the plots. Because the plots had to be thinned, an artificial condition was created and only qualitative judgment could be made concerning the performance of the test compound. In some instances the rotary tiller dug too deeply into the turf, thus exposing untreated soil in which crabgrass could be established; therefore, a judgment had to be made whether the crabgrass plants were grown in a deep hole, an untreated soil, or in the shallow rims.

Plots treated with l-ethyl-2,4',6'-triisopropylbenzyl alcohol l4 days after laying the sod were judged to have less crabgrass than the untreated seeded control plots. Of these, plots treated with l-ethyl-2',4,6-triisopropylbenzyl alcohol at 5 pounds per acre and 2 pounds per acre had some crabgrass plants only on the bottom of deep holes cut by the rotary tiller. The plots sprayed with l-ethyl-2 ',4'.6'-triisopropylbenzyl alcohol 58 days after the sod was laid were free of crabgrass at both the 2 pounds per acre and 5 pounds per acre rates.

The l-ethyl-2,4',6-triisopropylbenzyl alcohol used in these experiments was dissolved in a solvent mixture (90% acetone, 8% methanol, and 2% dimethylformamide by volume) and sprayed on the plots in 140 milliliters of solvent, each 40-square-feet area receiving 0.4l5 grams/pound/acre of l-ethyl-2',4',6'-triisopropylbenzyl alcohol.

Tests have been conducted to compare the response of johnsongrass, crabgrass and other plant species to pre-emergent applications of the following:

l. 1-ethyl-2,4,6'-triisopropylbenzyl alcohol,

2. Benzyl alcohol,

3. l-methyl-4'-isopropyl benzyl alcohol and 4. 3,4-dichloro-2-trichloromethylbenzyl alcohol The results of ratings after two weeks are presented below in Table 12 As before indicates no injury or control, and l0" indicates a complete kill.

Table l2 Rate.

(ompounds pound facrc C805 ANBG KTBG BNGS RICE JNGS l l l 9 U l() 2 U 3 1 HI 4 '9 3 U 8 4 H ll) 6 l 9 ll) Ill 8 ll) 9 2 9 [Z l l U 3 4 U U U I (I 3 3* U U U 4 (J U I U U U l() U U 2 U U U l T l U U U U U U I. (J U 2 U U U 4 U 2 3 U U U ll) U U l U U U [-l l (l U l U U U I l l l U U 3 4 2 Z 3 2 l 4 H) 5 4 7 3 Z 5 Rating auumnli Ius-puor germination From the foregoing, the superiority of compound l to other compounds mentioned in the prior art is apparent, particularly with reference to the control of crabgrass.

The especial effectiveness of compound l l-ethyl- 2',4',6'-triisopropylbenzyl alcohol, as compared with other compounds of similar chemical structure, can be seen from the following Table 13 which summarizes data presented above in the places indicated. In this Table, compound l is compared with the following: (5) l-methyl-2',4',6'-triis0propylbenzyl alcohol, (6) l-npropyl2',4',6triisopropylbenzyl alcohol, and (7) L2- ,4 ,6 -tetraisopropylbenzyl alcohol.

Table 1?:

Com- Rate of Application, JNGS YLFX BNGS CBGS pound Pounds Per Acre 1 l0 6 9 9 ll) 5 9' 9 9 IU 2 8' 8' 8' [U l 8 8 5' 9' 5 l U 3" 7 6" l U" 5 4 7 7 9 2 U 3 5 3 l O" 3 2 3 6 lU 2 9 4 9 5 U" 9 5 9" 2 U" 5" 2 8 l U U" U 5" 7 IO U 9" 7" ll) 5 U 6 3 9 2 a n 1: l U l O 2" Sec ratings, 20 days, Table 2 *Scc ratings, 2U days, Table I "See ratings, 23 days, Table 4 Sci: ratings, l3 days, Table 7 "Sec ratings. Zll days, Table J *c ratings, l3 Lla'l,1llhll2 8 Sec ratings, 23 days. Table 6 Sue ratings, 23 days, Table 5 The forgoing Table l3 shows an especially better herbicidal effectiveness for the compound l especially at low rates of application on the order of l or 2 pounds per acre. At rates that low, compound l consistently outperforms compounds 5, 6, and 7, which are (chemically speaking) adjacent homologs.

While I have shown and described herein certain embodiments of my invention, I intend to cover as well any change or modification therein that may be made without departing from its spirit and scope.

I claim:

1. A composition of matter selected from the group consisting of l-ethyl-2,4',6'-triisopropylbenzyl alcohol, l-ethyl-2',4,5'-triisopropylbenzyl alcohol, and mixtures therof.

2. l-Ethyl 2',4',6'-triisopropylbenzyl alcohol.

3. l-Ethyl 2,4',5'-triisopropylbenzyl alcohol. 

1. A COMPOSITION OF MATTER SELECTED FROM THE GROUP CONSISTING OF 1 -ETHYL-2'',4'',6''-TRISORPYLBENZYL ALCOHOL, 1-ETHYL2'',4'',5''-TRISORPYLBENZYL ALCOHOL, AND MIXTUREA THEREOF.
 2. 1-Ethyl - 2'',4'',6''-triisopropylbenzyl alcohol.
 3. 1-Ethyl - 2'',4'',5''-triisopropylbenzyl alcohol. 